Zinc is the twenty-fourth most abundant element in the earth's crust and finds many industrial applications, the most important being the oxidation-resistant treatment of iron surfaces, and others being in various fields, including topical medicines, chemical reagents, etc.
Zinc is not found in the metallic state in nature. Its chief ore is zinc blend or sphalerite (ZnS) which is the source of ninety percent of the zinc produced today. The zinc production methods employed today necessitate high treatment costs and consequently zinc metal producers demand high-grade concentrates.
There are two main methods of zinc recovery from its ores, i.e., thermal reduction and electrolytic deposition, the latter requiring the availability of relatively inexpensive electrical power in view of the fact that the production of one ton of zinc requires approximately 4500 kilowatt-hours. The purest zinc (99.99%) is achieved by the electrolytic methods.
The current world production of zinc is about 3,800,000 metric tons per year, 47% by electrolytic methods and the balance by thermal methods.
The thermal methods involve the following general reactions: ##STR1##
The electrolytic methods generally involve the following reactions: ##STR2##
Electrolytic zinc plants utilize four operations: (1) roasting of zinc sulfide concentrate; (2) leaching of the roasted concentrate or calcine to extract the soluble zinc; (3) purification of the resulting solution; and (4) electrolysis of the solution to obtain metallic zinc.
Zinc impure electrolyte typically contains impurities of copper, cobalt, nickel and cadmium that are detrimental to the plating of zinc and must be removed--or at least reduced to an acceptably low concentration--prior to electrolysis. In past practice, the cobalt class of impurities were removed by a hot copper sulfate/arsenic trioxide/zinc dust first stage impure electrolytic purification.
The precise mechanism of the hot copper sulfate/arsenic trioxide/zinc dust purification technique is not thoroughly understood. However, a plausible explanation is as follows: zinc dust displaces copper and nickel from solution, and it is believed that the arsenic and copper are precipitated as a metallic couple. Zinc dust ordinarily does not displace cobalt and nickel from solution, but in the presence of the copper-arsenic couple, these metals are quantitatively precipitated. The copper sulfate and arsenic trioxide are added to the impure electrolyte to provide the metallic couple, however if the copper content of the electrolyte is sufficiently high, copper sulfate need not be added.
The by-product of the purification procedure is a cement copper cake residue containing, in addition to copper, varying amounts of zinc, cadmium, cobalt, nickel and arsenic. The market value of the cake is primarily dependent on the percentage of copper contained therein.
There are several disadvantages to the above described purification procedure.
(1) The process requires the addition of arsenic trioxide and possibly copper sulfate, which affects the economics of the overall process.
(2) The cement copper cake residue, because of its arsenic content, has a greatly reduced market value.
(3) The zinc, cadmium and cobalt values in the cement copper cake are not reflected in the market value of the latter and consequently reflect losses in the overall process economics.
U.S. Pat. No. 4,049,514 discloses a process that relates to the electrolytic production of zinc metal and involves the treatment of the cement copper cake to provide a treated cement copper cake upgraded in its copper content, and a copper arsenate product which is employed in the purification of the impure electrolyte. The copper arsenate is employed in the electrolyte purification process as a substitute for the more conventional copper sulfate and arsenic trioxide reagents discussed above.
Upgrading of cement copper cake and recovery of arsenic is accomplished in the process disclosed by the cited patent in four basic operations: (1) acid leaching; (2) cobalt removal; (3) caustic leach; and (4) arsenic removal. The acid leach is conducted under optimum conditions for the dissolution of zinc, cadmium and cobalt while at the same time suppressing copper extraction. The solution and residue of the acid leach are separated by filtration for further processing. In order to make a zinc/cadmium solution suitable for recycling to the zinc plant, cobalt is removed from the acid leach solution. The copper and arsenic containing residue from the acid leach is subjected to a caustic leach to dissolve the arsenic. The caustic leach slurry is then filtered. This leaves a residue containing 60 to 70 percent copper and less than 1 percent arsenic providing an improved marketable product having an increased copper content.
In accordance with this invention, an improved process is provided for the treatment of impure zinc electrolyte wherein the cement copper cake produced by the impure electrolyte purification step, is treated by an acid leach and then caustic leach, to provide a cement copper cake residue upgraded in copper content, as well as an arsenic containing caustic leach filtrate. Zinc arsenate is precipitated from the arsenic containing caustic leach filtrate with zinc containing spent electrolyte or zinc neutral. The zinc arsenate precipitate is employed in the purification of impure zinc electrolyte as a substitute for copper arsenate, or the copper sulfate arsenic trioxide reagents employed by known zinc electrolyte purification processes. The zinc arsenate filtrate is employed in the precipitation of jarosite residue as a substitute for sodium carbonate and copper arsenate filtrate.
Significantly, the use of zinc arsenate during the electrolyte purification step reduces the necessity of purchasing reagents from outside sources and, therefore reduces the cost of the over-all zinc electrolyte purification process. More specifically conventional zinc electrolyte purification processes employ copper sulfate and arsenic trioxide reagents which must be purchased from outside sources which increases the cost of the purification process. Although, as will be discussed below, a minor amount of arsenic trioxide may, in some instances, be required during the electrolyte purification step of this invention, the amount of arsenic trioxide employed is either totally eliminated or greatly reduced relative to conventional purification processes, and the purchase of copper sulfate is not required. Moreover, although U.S. Pat. No. 4,049,514 discloses a process employing copper arsenate precipitated from caustic leach filtrate, the copper employed to precipitate the copper arsenate is copper sulfate--a reagent which also must be purchased from outside sources. By way of contrast, this invention provides a more economic and efficient process for the purification of impure zinc electrolyte wherein the zinc arsenate is precipitated from the caustic leach filtrate employing zinc neutral or spent zinc electrolyte which are available purification plants as internal products of the zinc electrolysis process and, hence, the purchase of copper sulfate required by the process disclosed by U.S. Pat. No. 4,049,514 is not required.
The process of this invention comprises the step of: (1) electrolyte purification employing zinc arsenate obtained from the caustic leach filtrate. This step results in the formation of the cement copper cake which contains primarily copper, zinc, cadmium, cobalt, nickel and arsenic (2) acid leaching of the cement cake to provide a residue, enriched in copper and containing arsenic, and a filtrate containing zinc, cadmium and cobalt impurities; (3) removal of cobalt from the acid leach filtrate to provide a zinc containing solution suitable for electrolysis; (4) caustic leach of the acid leach residue to provide a residue rich in copper and an arsenic containing filtrate, (5) treatment of the arsenic containing filtrate from the caustic leach step to provide zinc arsenate. The zinc arsenate is then employed with zinc dust in the electrolytic purification step.